KR101458953B1 - Method of forming phase change material layer using Ge(Ⅱ) source, and method of fabricating phase change memory device - Google Patents

Abstract

A method for forming a phase change material film using a Ge (II) source and a method for manufacturing a phase change memory device are provided. In the reaction chamber, NR ₁ R ₂ R ₃ (wherein R ₁ , R ₂ And R ₃ are each independently _{H, CH 3, C 2 H} 5, C 3 H 7, C 4 H 9, Si (CH 3) 3, NH 2, NH (CH 3), N (CH 3) 2, NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ ). A Ge (II) source is supplied as a first source into the reaction chamber. A second source is supplied into the reaction chamber to form a Ge-containing phase change material film. The Ge (Ⅱ) source has improved reactivity compared to the Ge (Ⅳ) source and can reduce the deposition temperature when forming the phase change material film. Furthermore, by using the reactive gas represented by NR ₁ R ₂ R ₃ , the reactivity of the reactive gas with the Ge (Ⅱ) source can be improved and the deposition rate of the phase change material film can be improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a phase change material using a Ge (II) source and a method for fabricating a phase change memory device using the Ge (II)

The present invention relates to a thin film forming method and a memory device manufacturing method, and more particularly, to a method for forming a phase change material film using a Ge (II) source and a method for manufacturing a phase change memory element.

A phase change material such as a chalcogenide material is a material having a crystalline state and an amorphous state in accordance with a change in temperature, State resistivity. This property of the phase-change material makes it possible to apply the phase-change material as a memory element, and the use of the phase-change material as a memory element is a phase-change random access memory (PRAM) which has been recently studied.

The unit cell of the PRAM includes an access device and a phase change resistor. The phase change resistor generally has a phase change material pattern disposed between a lower electrode and an upper electrode, and the access element is electrically connected to the lower electrode.

Figure 1 is a graph illustrating a method for performing a set or reset programming for a phase change resistor.

Referring to FIG. 1, when a phase change material film in an amorphous state is first heated for a certain time at a temperature between a crystallization temperature (Tx) and a melting point (Tm) and then cooled, The state changes to a crystalline state (set programming). On the other hand, when the phase change material film is heated to a temperature above the melting point (Tm) and rapidly cooled, the phase change material film changes from a crystalline state to an amorphous state (reset programming).

At this time, heating the phase-change material film to a temperature between the crystallization temperature and the melting point or to a temperature equal to or higher than the melting point is determined by the amount of the write current flowing through the access element. More specifically, when a write current flows through the access element, joule heat is generated at the interface between the lower electrode electrically connected to the access element and the phase change material layer. It can be determined according to the amount of current.

In order to apply a relatively large write current during reset programming, the size of the access element must also be increased, which is an obstacle to an increase in device integration. In order to solve this problem, a method of increasing an effective current density of the write current by reducing a contact area between the lower electrode and the phase change material film has been studied. One of such methods is to form a fine via hole exposing a part of the lower electrode and filling the via hole with a phase change material to form a phase change material film, thereby reducing the contact area between the lower electrode and the phase change material film . However, since the phase change material film is generally formed by a sputtering method, it is very difficult to fill the via hole without a void due to the poor step coverage characteristics of the film formed by the sputtering method.

SUMMARY OF THE INVENTION The present invention provides a method of forming a phase change material layer having a good step coverage at a low temperature and a method of manufacturing a phase change memory device using the same.

According to an aspect of the present invention, there is provided a method for forming a phase change material layer. A reaction gas represented by the following formula (1) is fed into the reaction chamber. A Ge (II) source is supplied as a first source into the reaction chamber. A second source is supplied into the reaction chamber to form a Ge-containing phase change material film.

≪ Formula 1 >

NR ₁ R ₂ R ₃

In Formula 1, R ₁ and R ₂ And R ₃ are each independently _{H, CH 3, C 2 H} 5, C 3 H 7, C 4 H 9, Si (CH 3) 3, NH 2, NH (CH 3), N (CH 3) 2, NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ .

The reaction gas may be one selected from the group consisting of ammonia, primary amine, and hydrazine.

The Ge (II) source may comprise an amide ligand, a phosphanido ligand, an alkoxide ligand, or a thiolate ligand. Specifically, the Ge (II) source may be any of the sources represented by the following formulas (2) to (4).

R ₁ R ₂ X ₁ -Ge- X ₂ R ₃ R ₄

In Formula 2, X ₁ And X ₂ are each independently N or P, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen; A C ₁ to C ₁₀ alkyl group; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefinic groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylenic group of C ₂ to C ₁₃ ; Allenic group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); Amide ligand (NR ₅ R ₆ , R ₅ and R ₆ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group); SiR ₇ R ₈ R _{9 wherein} R ₇ , R ₈ and R ₉ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or _two or more of R ₁ , R ₂ , R ₃ and R ₄ are chemically bonded to form a ring system.

R _{1 is} Y ₁ -Ge-Y ₂ R ₂

In Formula 3, Y ₁ And Y < ₂ > are each independently O or S, and R < _{1 &} And R < ₂ > are each independently selected from the group consisting of hydrogen; Alkyl group of C ₁ ~ C _10; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefin groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylene group of C ₂ to C ₁₃ ; Allene group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); An amide ligand (NR ₃ R ₄ , R ₃ and R ₄ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allylene group); SiR ₅ R ₆ R _{7 wherein} R ₅ , R ₆ and R ₇ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or R ₁ and R ₂ are chemically bonded to form a ring system.

R ₁ R ₂ X-Ge-YR ₃

In Formula 4, X is N or P, Y is O or S, R ₁ , R _2, and R ₃ are each independently hydrogen; Alkyl group of C ₁ ~ C _10; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefin groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylene group of C ₂ to C ₁₃ ; Allene group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); An amide ligand (NR ₄ R ₅ , R ₄ and R ₅ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group); SiR ₆ R ₇ R _{8 wherein} R ₆ , R ₇ and R ₈ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or R ₁ , R ₂ And R < ₃ > are chemically bonded to form a ring system.

According to an aspect of the present invention, there is provided a method of forming a phase change material layer. A Ge (II) source is supplied as a first source into the reaction chamber. A second source is supplied into the reaction chamber to form a Ge-containing phase change material film.

The Ge (II) source may be any one of the following formulas 5 to 17.

In Formula 5, X ₁ And X ₂ are each independently N or _{P, R 1, R 2,} R 3 and R ₄ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ C ₁₃ , or an allylene group.

In Formula 6, X ₁ And X ₂ are each independently N or P and R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, .

Wherein X ₁ , X ₂ , X ₃ and X ₄ are each independently N or P and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ And R ₆ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allene group.

In Formula 8, X ₁ and X ₂ are each independently N or P, and, Y ₁ and Y ₂ are each independently O or _{S, R 1, R 2,} R 3, R 4, R 5, R 6 , R ₇ and R ₈ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group.

Wherein X ₁ , X ₂ , X ₃ and X ₄ are each independently N or P and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allene group.

In Formula _{10, X 1, X 2,} X 3 and X ₄ are each independently N or _{P, R 1, R 2,} R 3, R 4, R 5 and R ₆ are independently hydrogen, C ₁ each An alkyl group having ₁ to ₁₀ carbon atoms, an olefin group having ₂ to ₁₂ carbon atoms, an acetylene group or an allene group having ₂ to ₁₃ carbon atoms.

In Formula 11, X ₁ and X ₂ are each independently N or P, Y ₁ and Y ₂ are each independently O or S, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, A C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allylene group.

In Formula 12, Y ₁ and Y ₂ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ of An acetylene group or an allylene group of C < ₁₃ >

In Formula 13, Y ₁ and Y ₂ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ of An acetylene group or an allylene group of C < ₁₃ >

In Formula _{14, Y 1, Y 2,} Y 3 and Y ₄ are each independently O or _{S, R 1, R 2,} R 3, R 4, R 5 and R ₆ is hydrogen, C ₁ are each independently An alkyl group having ₁ to ₁₀ carbon atoms, an olefin group having ₂ to ₁₂ carbon atoms, an acetylene group or an allene group having ₂ to ₁₃ carbon atoms.

In Formula 15, X ₁ and X ₂ are each independently N or P, Y ₁ and Y ₂ are each independently O or S, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen, A C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allylene group.

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ An olefin group, an acetylene group or an allene group of C ₂ to C ₁₃ .

Wherein X is N or P, Y is O or S, R ₁ , R ₂ and R ₃ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, An acetylene group or an allylene group of C ₂ to C ₁₃ .

According to another aspect of the present invention, there is provided a method for fabricating a phase change memory device. The substrate on which the lower electrode is formed is loaded in the reaction chamber. A Ge-containing phase change material film is formed on the lower electrode by supplying a reaction gas represented by the formula (1), a first source Ge (II) source and a second source into the reaction chamber loaded with the substrate. An upper electrode is formed on the phase change material film.

Before forming the phase change material layer, a mold insulating layer having a via hole exposing a part of the lower electrode may be formed on the lower electrode. In this case, the phase change material film can be formed in the via hole.

In one embodiment, the phase change material film may fill the via hole.

In another embodiment, the phase change material film may be formed on the side wall of the via hole. Anisotropically etching the phase change material layer to form a phase change material spacer on a sidewall of the via hole; filling a buffer insulation layer in a via hole formed with the phase change material spacer; The buffer insulating film can be planarized and etched. In this case, the upper electrode may be formed on the phase change material spacer.

As described above, according to the present invention, firstly, the Ge (II) source has improved reactivity as compared with the Ge (IV) source, and can reduce the deposition temperature when forming the phase change material film. The phase change material film deposited at such a low temperature has a smaller grain size than the phase change material film formed at a high processing temperature. Therefore, the step coverage of the phase change material film is improved, so that the phase change material film can be formed on the side wall of the contact hole without blocking the entrance of the contact hole, and the contact hole can be filled without voids.

Second, NR ₁ R ₂ R ₃ , wherein R ₁ , R ₂ And R ₃ are each independently _{H, CH 3, C 2 H} 5, C 3 H 7, C 4 H 9, Si (CH 3) 3, NH 2, NH (CH 3), N (CH 3) 2, NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ ), the reactivity between the reactive gas and the Ge (Ⅱ) source is improved to improve the deposition rate of the phase change material film .

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the thicknesses of the layers and regions are exaggerated for clarity. Like reference numerals designate like elements throughout the specification.

Phase change Material film  How to form

2 is a flow chart illustrating a method of forming a phase change material film according to an embodiment of the present invention.

Referring to FIG. 2, a substrate is loaded in a reaction chamber (S10). Wherein the substrate is a dielectric film made of silicon oxide, titanium oxide, aluminum oxide (Al2O3), zirconium oxide, or hafnium oxide; A conductive film made of titanium (Ti), titanium nitride (TiN), aluminum, thallium (Ta), thallium nitride (TaN), or titanium aluminum nitride (TiAlN); Or a semiconductor film made of silicon or silicon carbide (SiC).

The reaction chamber may be a cold wall type or a hot wall type. The cold-walled reaction chamber may include a substrate stage having a heating wire and a showerhead positioned on the substrate stage. The substrate may be disposed on the substrate stage. The cold wall type reaction chamber may be a single type. On the other hand, the thermal wall type reaction chamber has a heat line disposed in its wall. A plurality of substrates may be vertically stacked in the thermal-walled reaction chamber. Such a reaction chamber may be a vertical & batch type.

A reaction gas represented by the following formula (1) may be fed into the reaction chamber (S20).

≪ Formula 1 >

NR ₁ R ₂ R ₃

In Formula 1, R ₁ and R ₂ And R ₃ are each independently _{H, CH 3, C 2 H} 5, C 3 H 7, C 4 H 9, Si (CH 3) 3, NH 2, NH (CH 3), N (CH 3) 2, NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ .

The reactive gas may be a reactive gas having an NH ₂ group. Further, the reaction gas may be one gas selected from the group consisting of ammonia, primary amine, and hydrazine. The Ge (II) source may be supplied as the first source into the reaction chamber before, after, or simultaneously with the supply of the reactive gas (S30). In the Ge (II) source, "II" means that the oxidation state of Ge is +2. The Ge (II) source can be supplied with the carrier gas. The carrier gas may contain argon (Ar), helium (He) or nitrogen (N ₂ ) as an inert gas. Alternatively, the Ge (II) source may be dissolved using a solvent, and then vaporized rapidly in a vaporizer to be supplied into the reaction chamber.

The Ge (II) source may have an amide ligand, a phosphanido ligand, an alkoxide ligand, or a thiolate ligand.

The Ge (II) source having an amide ligand and / or a phosphandido ligand can be represented by the following formula (2).

(2)

R ₁ R ₂ X ₁ -Ge- X ₂ R ₃ R ₄

In Formula 2, X ₁ And X ₂ are each independently N or P, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen; A C ₁ to C ₁₀ alkyl group; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefinic groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylenic group of C ₂ to C ₁₃ ; Allenic group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); Amide ligand wherein each of NR ₅ R ₆ , R ₅ and R ₆ is independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group ); SiR ₇ R ₈ R _{9 wherein} R ₇ , R ₈ and R ₉ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or _two or more of R ₁ , R ₂ , R ₃ and R ₄ are chemically bonded to form a ring system.

A Ge (II) source having an alkoxide ligand and / or a thiolate ligand can be represented by the following formula (3).

(3)

R _{1 is} Y ₁ -Ge-Y ₂ R ₂

In Formula 3, Y ₁ And Y < ₂ > are each independently O or S, and R < _{1 &} And R < ₂ > are each independently selected from the group consisting of hydrogen; Alkyl group of C ₁ ~ C _10; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefin groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylene group of C ₂ to C ₁₃ ; Allene group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); An amide ligand (NR ₃ R ₄ , R ₃ and R ₄ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allylene group); SiR ₅ R ₆ R _{7 wherein} R ₅ , R ₆ and R ₇ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or R ₁ and R ₂ are chemically bonded to form a ring system.

Amide ligand and phosphandido ligand; And a Ge (II) source having any one of an alkoxide ligand and a thiolate ligand can be represented by the following general formula (4).

≪ Formula 4 >

R ₁ R ₂ X-Ge-YR ₃

In Formula 4, X is N or P, Y is O or S, R ₁ , R _2, and R ₃ are each independently hydrogen; Alkyl group of C ₁ ~ C _10; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefin groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylene group of C ₂ to C ₁₃ ; Allene group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); An amide ligand (NR ₄ R ₅ , R ₄ and R ₅ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group); SiR ₆ R ₇ R _{8 wherein} R ₆ , R ₇ and R ₈ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or R ₁ , R ₂ And R < ₃ > are chemically bonded to form a ring system.

Specific examples of the Ge (II) source represented by the formula (2) may be a Ge (II) source represented by the following chemical formulas 5 to 11.

≪ Formula 5 >

In Formula 5, X ₁ And X ₂ are each independently N or _{P, R 1, R 2,} R 3 and R ₄ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ C _{13 &lt}; / RTI >

(6)

In Formula 6, X ₁ And X ₂ are each independently N or P and R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, .

≪ Formula 7 >

Wherein X ₁ , X ₂ , X ₃ and X ₄ are each independently N or P and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ And R ₆ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allene group.

(8)

In Formula 8, X ₁ and X ₂ are each independently N or P, and, Y ₁ and Y ₂ are each independently O or _{S, R 1, R 2,} R 3, R 4, R 5, R 6 , R ₇ and R ₈ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group.

≪ Formula 9 >

Wherein X ₁ , X ₂ , X ₃ and X ₄ are each independently N or P and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allene group.

≪ Formula 10 >

In Formula _{10, X 1, X 2,} X 3 and X ₄ are each independently N or _{P, R 1, R 2,} R 3, R 4, R 5 and R ₆ are independently hydrogen, C ₁ each An alkyl group having ₁ to ₁₀ carbon atoms, an olefin group having ₂ to ₁₂ carbon atoms, an acetylene group or an allene group having ₂ to ₁₃ carbon atoms.

≪ Formula 11 >

In Formula 11, X ₁ and X ₂ are each independently N or P, Y ₁ and Y ₂ are each independently O or S, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, A C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allylene group.

Specific examples of the Ge (II) source represented by the formula (3) may be Ge (II) source represented by the following formulas 12 to 16.

≪ Formula 12 >

In Formula 12, Y ₁ and Y ₂ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ of An acetylene group or an allylene group of C < ₁₃ >

≪ Formula 13 >

In Formula 13, Y ₁ and Y ₂ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ of An acetylene group or an allylene group of C < ₁₃ >

≪ Formula 14 >

In Formula _{14, Y 1, Y 2,} Y 3 and Y ₄ are each independently O or _{S, R 1, R 2,} R 3, R 4, R 5 and R ₆ is hydrogen, C ₁ are each independently An alkyl group having ₁ to ₁₀ carbon atoms, an olefin group having ₂ to ₁₂ carbon atoms, an acetylene group or an allene group having ₂ to ₁₃ carbon atoms.

≪ Formula 15 >

In Formula 15, X ₁ and X ₂ are each independently N or P, Y ₁ and Y ₂ are each independently O or S, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen, A C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allylene group.

≪ Formula 16 >

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ An olefin group, an acetylene group or an allene group of C ₂ to C ₁₃ .

A specific example of the Ge (II) source represented by the formula (4) may be a Ge (II) source represented by the following formula (17).

≪ Formula 17 >

Wherein X is N or P, Y is O or S, R ₁ , R ₂ and R ₃ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, An acetylene group or an allylene group of C ₂ to C ₁₃ .

These Ge (Ⅱ) sources are less covalent between Ge and ligands than Ge (Ⅳ) sources, and have fewer steric hindrance by ligands because of the small number of ligands bound to Ge . Even when the number of ligands of the Ge (II) source and the Ge (IV) source is the same, the dative bonding among the Ge-ligand bonds of the Ge (II) source can be easily broken by heat in the reaction chamber, The number of ligands bound to the steric hindrance decreases and the steric hindrance is less likely to be transformed into a structure. Therefore, the Ge (II) source has improved reactivity as compared with the Ge (IV) source, and can reduce the film forming temperature when forming the phase change material film.

Specifically, the Ge (II) sources represented by the above-described formulas 5, 6, 12, 13, and 17 have fewer steric hindrance because two Ge-bonded elements are present. The Ge (II) sources represented by the above formulas 7, 8, 9 and 14 have four elements bonded to Ge, but two ligands located on both sides of Ge are located on almost the same plane, Is sterically opened. The Ge (II) sources represented by the above-described formulas 10, 11, 15, and 16 have four Ge-bonded elements, but as shown in the following reaction formulas 1 to 4, Ge- The coordination bonds are easily broken and the elements bonded to Ge can be transformed into two states.

In the above scheme _{1, X 1, X 2,} X 3 and X ₄ are each independently N or _{P, R 1, R 2,} R 3, R 4, R 5 and R ₆ are independently hydrogen, C ₁ each An alkyl group having ₁ to ₁₀ carbon atoms, an olefin group having ₂ to ₁₂ carbon atoms, an acetylene group or an allene group having ₂ to ₁₃ carbon atoms.

Wherein X ₁ and X ₂ are each independently N or P, Y ₁ and Y ₂ are each independently O or S, and R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, A C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allylene group.

Wherein X ₁ and X ₂ are each independently N or P, Y ₁ and Y ₂ are each independently O or S, and R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, A C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allylene group.

Wherein Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ An olefin group, an acetylene group or an allene group of C ₂ to C ₁₃ .

The second source may be further supplied to the reaction chamber before, after, or simultaneously with the supply of the reactive gas and the Ge (II) source (S40). As a result, a phase change material film containing Ge is formed on the substrate (S50). The second source may also be supplied with the carrier gas. The carrier gas may contain argon (Ar), helium (He) or nitrogen (N ₂ ) as an inert gas. Alternatively, the second source may be dissolved using a solvent, and then vaporized rapidly in a vaporizer to be supplied into the reaction chamber.

The second source may be at least one source selected from the group consisting of Te source, Sb source, Bi source, As source, Sn source, O source, Au source, Pd source, Se source, Ti source and S source. At this time, the Ge-containing phase change material layer may be a Ge-Sb-Te layer, a Ge-Te layer, a Ge-Sb layer, a Ge-Bi-Te layer, a Ge- Te-Sn-O film, Ge-Te-Sn-Au film, Ge-Te-Sn-Pd film, Ge- Ge-Sb- (Se, Te) film, or Ge-Sb-Te-S film. The Ge-containing phase change material film may contain N, O, Bi, Sn, B, Si, or a combination thereof as an impurity.

When the Te source and / or the Sb source is supplied as the second source, the Ge-containing phase change material film formed on the substrate may be a Ge-Sb-Te film, a Ge-Te film or a Ge-Sb film. In this case, the Te source is _{Te (CH 3) 2, Te} (C 2 H 5) 2, Te (nC 3 H 7) 2, Te (iC 3 H 7) 2, Te (tC 4 H 9) 2, _{Te (iC 4 H 9) 2} , Te (CH = CH 2) 2, Te (CH 2 CH = CH 2) 2, Te [N (Si (CH 3) 3) 2] may be _2, wherein the Sb source It is _{Sb (CH 3) 3, Sb} (C 2 H 5) 3, Sb (iC 3 H 7) 3, Sb (nC 3 H 7) 3, Sb (iC 4 H 9) 3, Sb (tC 4 H 9 _{) 3, Sb (N (CH} 3) 2) 3, Sb (N (CH 3) (C 2 H 5)) 3, Sb (N (C 2 H 5) 2) 3, Sb (N (iC 3 H ₇ ) ₂ ) ₃ or Sb [N (Si (CH ₃ ) ₃ ] ₂ ] ₃ .

The Ge (II) source may react with the reactive gas to form a Ge (II) intermediate in which the ligands around the Ge are substituted by the reactive gas. Wherein said Ge (II) intermediate is selected from the group consisting of two NR ₁ R ₂ moieties around Ge, wherein R ₁ and R ₂ are each independently H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , Si (CH ₃ ) ₃ , NH ₂ , NH (CH ₃ ), N (CH ₃ ) ₂ , NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ ligands. The reactivity between the Ge (II) source and the reactive gas is improved compared to the reactivity of the Ge (IV) source and the reactive gas, and the reaction temperature can be reduced. For example, the reaction formula of the Ge (II) source represented by Formula 5 and ammonia to form a Ge (II) intermediate is as follows.

In the above Reaction Scheme 5, X ₁ And X ₂ are each independently N or _{P, R 1, R 2,} R 3 and R ₄ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ C _{13 &lt}; / RTI >

The Ge (II) intermediate may react with the second source to form a Ge-containing phase change material film. As an example, the reaction formula in which the Ge (II) intermediate produced according to Reaction Scheme 5 reacts with the Te source to form a phase change material is shown in the following Reaction Scheme 6.

In the above Reaction Scheme 6, R 'is CH (CH ₃ ) ₂ .

The Ge (II) intermediate is highly reactive with the second source. In addition, the Ge (II) intermediate has a small steric hindrance by the ligands as well as the Ge (II) source. As a result, the reaction temperature can be further reduced. As a result, the deposition temperature of the Ge-containing phase change material film can be reduced. Specifically, the deposition temperature of the Ge-containing phase change material film can be lowered to less than 300 캜. Further, the deposition temperature of the Ge-containing phase change material film can be reduced to 200 캜. The phase change material film deposited at such a low temperature has a smaller grain size than the phase change material film formed at a high processing temperature. Therefore, the step coverage of the phase change material film is improved, so that the phase change material film can be formed on the side wall of the contact hole without blocking the entrance of the contact hole, and the contact hole can be filled without voids.

The Ge-containing phase change material layer may be formed using CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition). Therefore, the step coverage of the Ge-containing phase change material film can be further improved.

3 is a gas pulsing diagram for forming a Ge-Sb-Te film using a chemical vapor deposition method.

Referring to FIG. 3, a Ge (II) source, a Sb source, and a Te source are simultaneously supplied while a carrier gas and a reaction gas are supplied into the reaction chamber. Wherein the reactive gas is NR ₁ R ₂ R ₃ , wherein R ₁ , R ₂ And R ₃ are each independently _{H, CH 3, C 2 H} 5, C 3 H 7, C 4 H 9, Si (CH 3) 3, NH 2, NH (CH 3), N (CH 3) 2, NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ ). Specifically, the reaction gas may be ammonia, a primary amine or hydrazine. The first carrier gas may contain argon (Ar), helium (He) or nitrogen (N ₂ ) as an inert gas. The Ge (II) source may have an amide ligand, a phosphandido ligand, an alkoxide ligand or a thiolate ligand. The reaction between the Ge (II) source and the reactive gas causes the ligands around Ge to react with NR ₁ R ₂ where R ₁ and R ₂ are each independently H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C the ligand represented by _{4 H 9, Si (CH 3} ) 3, NH 2, NH (CH 3), N (CH 3) 2, NH (C 2 H 5) or N (C ₂ H _{5) 2} Im) (II) intermediate, and the Ge (II) intermediate reacts with the Te source to form GeTe. In addition, the Te source and the Sb source react with each other to form Sb ₂ Te ₃ . The GeTe and Sb ₂ Te ₃ may form a Ge-Sb-Te film having a composition of Ge ₂ Sb ₂ Te ₅ . At this time, the reactivity between the Ge (II) source and the reactive gas and the reactivity between the Ge (II) intermediate and the Te source are improved, and the deposition temperature of GeTe can be reduced. The Ge (II) source, the Sb source and the Te source may be implanted in an amount of 10 to 1000 sccm, respectively, and may be implanted for 1 to 1000 seconds. The time at which the Ge (II) source, the Sb source, and the Te source are implanted into the chamber may be defined as a deposition time.

4 is a gas pulsing diagram for forming a Ge-Sb-Te film using atomic layer deposition.

Referring to FIG. 4, a Ge-Te film is formed by injecting a Ge (II) source and a Te source while supplying the first carrier gas and the first reactive gas into the reaction chamber for a time period of T 1. Wherein the first reactive gas is NR ₁ R ₂ R ₃ , wherein R ₁ , R ₂ And R ₃ are each independently _{H, CH 3, C 2 H} 5, C 3 H 7, C 4 H 9, Si (CH 3) 3, NH 2, NH (CH 3), N (CH 3) 2, NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ ). Specifically, the reaction gas may be ammonia, a primary amine or hydrazine. The first carrier gas may contain argon (Ar), helium (He) or nitrogen (N ₂ ) as an inert gas. The Ge (II) source may have an amide ligand, a phosphandido ligand, an alkoxide ligand or a thiolate ligand. The Ge (Ⅱ) source and the second ligand around the Ge and the first reaction gas to the reaction NR ₁ R ₂ (wherein, R ₁ And R ₂ are each independently _{H, CH 3, C 2 H} 5, C 3 H 7, C 4 H 9, Si (CH 3) 3, NH 2, NH (CH 3), N (CH 3) 2, (II) intermediate substituted with ligands represented by NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ , and the Ge (II) intermediate reacts with the Te source to form GeTe . At this time, the reactivity between the Ge (II) source and the first reactive gas and the reactivity between the Ge (II) intermediate and the Te source may be improved, and the deposition temperature of GeTe may be reduced.

Then, the Ge (II) source and the Te source, physically adsorbed by supplying the first carrier gas and the first reaction gas into the reaction chamber, are intercepted during the T2 time period, And unreacted Ge (II) source and Te source are removed (second stage).

The Sb source and the Te source are implanted to form an Sb-Te film, for example, Sb ₂ Te ₃ (Step 3) while supplying the second carrier gas and the second reactive gas into the reaction chamber for a time T ₃ . The second reactant gas may be independently selected from the group consisting of hydrogen (H ₂ ), oxygen (O ₂ ), ozone (O ₃ ), water vapor (H ₂ O), silane (SiH ₄ ) the first carrier gas may contain diborane, B ₂ H ₆ , hydrazine (N ₂ H ₄ ), a primary amine or ammonia (NH ₃ ), and the second carrier gas may be an inert gas, Argon (Ar), helium (He), or nitrogen (N ₂ ).

A Sb source and a Te source physically adsorbed by supplying the second carrier gas and the second reactive gas into the reaction chamber; And the unreacted Sb source and Te source are removed (Step 4).

A Ge-Sb-Te film having a composition of, for example, Ge ₂ Sb ₂ Te ₅ may be formed by repeating a cycle including the first to fourth steps. The Ge (II) source, the Sb source and the Te source may be implanted in an amount of 10 to 1000 sccm for 0.1 to 60 seconds.

Ge  contain Phase change Material film  Using the formation method Phase change  Method of manufacturing a memory device

5A and 5B are cross-sectional views illustrating a method of manufacturing a phase-change memory device according to an embodiment of the present invention.

Referring to FIG. 5A, a device isolation layer (not shown) is formed on a substrate 100 to define active regions. A gate insulating film 105 and a gate conductive film 110 are sequentially stacked on the active region and the gate conductive film 110 and the gate insulating film 105 are sequentially etched to form a gate electrode 110. [ A low concentration impurity region 101a adjacent to the gate electrode 110 is formed in the substrate 100 by doping impurities into the substrate 100 at a low concentration using the gate electrode 110 as a mask.

The gate spacer insulating film is stacked on the substrate 100 on which the lightly doped impurity region 101a is formed and the gate spacer insulating film is anisotropically etched to form gate spacers 115 on the sidewalls of the gate electrode 110. [ Thereafter, impurities are doped in the substrate 100 at a high concentration using the gate electrode 110 and the gate spacer 115 as a mask so that a high concentration (concentration) of the gate spacer 115 adjacent to the gate spacer 115 Thereby forming an impurity region 101b.

The lightly doped impurity region 101a and the heavily doped impurity region 101b form a source / drain region, and the lightly doped impurity region 101a and the heavily doped impurity region 101b, which are located at one side of the gate electrode 110, The pair forms the source region 102 and the pair of the low concentration impurity region 101a and the high concentration impurity region 101b located on the other side forms the drain region 103. The gate electrode 110, the source region 102, and the drain region 103 constitute a MOS transistor, and the MOS transistor serves as an access element. However, the access element is not limited to the MOS transistor, but may be a diode or a bipolar transistor.

A first interlayer insulating film 120 is formed on a substrate 100 on which the source and drain regions 102 and 103 are formed and the first interlayer insulating film 120 is penetrated through the first interlayer insulating film 120 A contact plug 125 to be connected to the drain region 103 is formed. The contact plug 125 may be formed of a tungsten film.

A lower electrode 135 is formed on the contact plug 125 so as to cover the contact plug 125. The lower electrode 135 may be formed of a titanium nitride film (TiN), a titanium aluminum nitride film (TiAlN), a tantalum nitride film (TaN), a tungsten nitride film (WN), a molybdenum nitride film (MoN), a niobium nitride film (TiN), a titanium boron nitride film (TiBN), a zirconium silicon nitride film (ZrSiN), a tungsten silicon nitride film (WSiN), a tungsten boron nitride film (WBN), a zirconium aluminum nitride film (ZrAlN), a molybdenum aluminum nitride film (TiON), a titanium aluminum oxynitride (TiAlON), a tungsten oxynitride (WON), or a tantalum (Ta) nitride film Or an oxynitride film (TaON).

A mold insulating layer 140 is formed on the lower electrode 135 and a via hole 140a is formed in the mold insulating layer 140 to expose a portion of the lower electrode 135. A hole spacer insulating layer is stacked on the substrate having the via hole 140a formed therein and the hole spacer insulating layer is anisotropically etched to expose the bottom electrode 135 in the via hole 140a. As a result, a hole spacer 145 is formed on the side wall in the via hole 140a. Therefore, the effective diameter of the via hole 140a may be smaller than the resolution limit of the photolithography process by the hole spacers 145. [

Subsequently, the phase change material layer 150 is deposited on the substrate on which the via hole 140a is formed. The phase change material film 150 can be formed using the method described with reference to FIG. 2 as a Ge-containing phase change material film. Therefore, the deposition temperature of the phase change material film 150 can be reduced to less than 300 ° C. Further, the deposition temperature of the phase change material layer 150 can be reduced to 200 캜. The phase change material film 150 deposited at such a low temperature has a smaller grain size than the phase change material film formed at a high processing temperature. Therefore, even when the effective diameter of the via hole 140a is very small, the phase change material layer 150 can fill the via hole 140a without voids.

Referring to FIG. 5B, the phase change material layer 150 is planarized to form a phase change material pattern 151. An upper electrode 160 is formed on the phase change material pattern 151. Planarization of the phase change material layer 150 may be performed using etch back or chemical mechanical polishing (CMP). As a result, a phase change resistor having a lower electrode 135, an upper electrode 160, and a phase change material pattern 151 disposed between the lower electrode 135 and the upper electrode 160 is formed.

6A, 6B, and 6C are cross-sectional views illustrating a method of manufacturing a phase-change memory device according to another embodiment of the present invention. The manufacturing method according to this embodiment is similar to the manufacturing method described with reference to Figs. 5A and 5B except for the following.

6A, a mold insulating layer 140 is formed on the lower electrode 135, and a via hole 140a is formed in the mold insulating layer 140 to expose a portion of the lower electrode 135. Referring to FIG. A phase change material layer 152 is deposited in the via hole 140a. The phase change material layer 152 is formed so as to cover the sidewalls of the via hole 140a without completely filling the via hole 140a. The phase change material film 152 can be formed using the method described with reference to FIG. 2 as a Ge-containing phase change material film. Therefore, the deposition temperature of the phase change material film 152 can be reduced to less than 300 캜. Further, the deposition temperature of the phase change material film 152 can be reduced to 200 캜. The phase change material film 152 deposited at such a low temperature has a smaller grain size than the phase change material film formed at a high processing temperature. Therefore, the side wall of the via hole can be conforma covered without blocking the upper portion of the via hole.

6B, the phase change material layer 152 is anisotropically etched until the lower electrode 135 is exposed to form a phase change material spacer 153 on the sidewall of the via hole 140a, The upper surface of the mold insulating film 140 is exposed. A buffer insulating layer 155 is formed on the exposed lower electrode 135 and the mold insulating layer 140. The buffer insulating layer 155 is formed to fill the via hole 140a. The side walls of the buffer insulating layer 155 are surrounded by the phase change material spacer 153 in the via hole 140a.

The substrate on which the buffer insulating layer 155 is formed is planarized to expose the upper surface of the phase change material spacer 153. As an example, it can be planarized to the broken line shown in the figure.

6C, an upper electrode 160 is formed on the phase change material spacer 153 on which the upper surface is exposed. As a result, a phase change resistor having a lower electrode 135, an upper electrode 160, and a phase change material spacer 153 disposed between the lower electrode 135 and the upper electrode 160 is formed. The contact area between the phase change material spacer 153 and the lower electrode 135 may be reduced as compared with the phase change material pattern described with reference to FIG. Therefore, the effective current density of the write current applied to the phase-change material spacer 153 can be further increased.

<Experimental Examples> examples>

<Experimental Example 1>

The substrate was loaded into the reaction chamber. In the reaction chamber, Ar 500 sccm of carrier and 100 sccm of NH ₃ as a reactor were supplied. 100 sccm of a Ge (II) source represented by the following Chemical Formula 18 was supplied into the reaction chamber to which Ar and NH ₃ were supplied. Simultaneously, Te (CH (CH ₃ ) ₂ ) ₂ of 100 sccm was supplied into the reaction chamber to form a GeTe film on the substrate. The supply time of the Ge (II) source and Te (CH (CH ₃ ) ₂ ) ₂ was 900 seconds. The heater setting temperature in the reaction chamber was 320 ° C.

<Experimental Example 2>

A GeTe film was formed on the substrate using the same method as Experimental Example 1, except that the heater setting temperature in the reaction chamber was 280 ° C.

<Experimental Example 3>

A GeTe film was formed on the substrate using the same method as Experimental Example 1, except that the heater setting temperature in the reaction chamber was 240 캜.

<Experimental Example 4>

A GeTe film was formed on the substrate using the same method as Experimental Example 1, except that the heater setting temperature in the reaction chamber was 200 ° C.

<Experimental Example 5>

The substrate was loaded into the reaction chamber. In the reaction chamber, Ar 500 sccm of carrier and 100 sccm of NH ₃ as a reactor were supplied. 100 sccm of Ge (II) source represented by the following Chemical Formula 19 was supplied into the reaction chamber to which Ar and NH ₃ were supplied. Simultaneously, Te (CH (CH ₃ ) ₂ ) ₂ of 100 sccm was supplied into the reaction chamber to form a GeTe film on the substrate. The supply time of the Ge (II) source and Te (CH (CH ₃ ) ₂ ) ₂ was 900 seconds. The heater setting temperature in the reaction chamber was 320 ° C.

<Experimental Example 6>

A GeTe film was formed on the substrate in the same manner as in Experimental Example 5, except that the heater setting temperature in the reaction chamber was 280 占 폚.

<Experimental Example 7>

A GeTe film was formed on the substrate using the same method as Experimental Example 5 except that the heater setting temperature in the reaction chamber was 240 캜.

<Experimental Example 8>

The substrate was loaded into the reaction chamber. Ar 500 sccm of the carrier Ar and 100 sccm of H ₂ as the reactor were fed into the reaction chamber. 100 sccm of the Ge (II) source represented by the above formula (18) was supplied into the reaction chamber to which Ar and H ₂ were supplied. Simultaneously, Te (CH (CH ₃ ) ₂ ) ₂ of 100 sccm was supplied into the reaction chamber to form a GeTe film on the substrate. The supply time of the Ge (Ⅱ) source and Te (CH (CH ₃ ) ₂ ) ₂ was 900 seconds. The heater setting temperature in the reaction chamber was 320 ° C.

<Experimental Example 9>

A GeTe film was formed on the substrate in the same manner as in Experimental Example 8, except that the heater setting temperature in the reaction chamber was 280 ° C.

<Experimental Example 10>

A GeTe film was formed on the substrate using the same method as Experimental Example 8 except that the heater setting temperature in the reaction chamber was 240 캜.

&Lt; Experimental Example 11 &

The substrate was loaded into the reaction chamber. Ar 500 sccm of the carrier Ar and 100 sccm of H ₂ as the reactor were fed into the reaction chamber. 100 sccm of the Ge (II) source represented by the above formula (19) was supplied into the reaction chamber to which Ar and H ₂ were supplied. Simultaneously, Te (CH (CH ₃ ) ₂ ) ₂ of 100 sccm was supplied into the reaction chamber to form a GeTe film on the substrate. The supply time of the Ge (II) source and Te (CH (CH ₃ ) ₂ ) ₂ was 900 seconds. The heater setting temperature in the reaction chamber was 320 ° C.

<Experimental Example 12>

A GeTe film was formed on the substrate by using the same method as in Experimental Example 11, except that the heater setting temperature in the reaction chamber was 280 ° C.

<Experimental Example 13>

A GeTe film was formed on the substrate by using the same method as in Experimental Example 11, except that the heater setting temperature in the reaction chamber was 240 DEG C. Comparative Example 1 [

The substrate was loaded into the reaction chamber. In the reaction chamber, Ar 500 sccm of carrier and 100 sccm of NH ₃ as a reactor were supplied. A Ge (Ⅵ) source of Ge (N (CH ₃ ) ₂ ) ₄ was supplied at 100 sccm into the reaction chamber to which Ar and NH ₃ were supplied. Simultaneously, Te (CH (CH ₃ ) ₂ ) ₂ of 100 sccm was supplied into the reaction chamber to form a GeTe film on the substrate. The supply time of the Ge (VI) source and Te (CH (CH ₃ ) ₂ ) ₂ was 900 seconds. The heater setting temperature in the reaction chamber was 320 ° C.

&Lt; Comparative Example 2 &

A GeTe film was formed on the substrate using the same method as in Comparative Example 1, except that the heater set temperature in the reaction chamber was 280 ° C.

Table 1 below shows the main experimental conditions and the deposition rate of the GeTe film according to Experimental Examples 1 to 13 and Comparative Examples 1 and 2.

<Table 1>

Ge Source Reaction gas Inside the reaction chamber
Heater set temperature
(° C) Sb ₂ Te ₃ film
Deposition rate
(Å / min) Experimental Example 1 Ge (Ⅱ) source
18 NH ₃ 320 12 Experimental Example 2 280 10 Experimental Example 3 240 7 Experimental Example 4 200 3 Experimental Example 5 Ge (Ⅱ) source
Formula 19 320 8 Experimental Example 6 280 4 Experimental Example 7 240 2 Comparative Example 1 Ge (Ⅳ) source
_{Ge (N (CH 3) 2} ) 4 320 Deposited Comparative Example 2 280 No deposition Experimental Example 8 Ge (Ⅱ) source
18 H ₂ 320 4 Experimental Example 9 280 0.7 Experimental Example 10 240 0.1 Experimental Example 11 Ge (Ⅱ) source
Formula 19 320 3 Experimental Example 12 280 0.8 Experimental Example 13 240 0.1

Referring to Table 1, when the reaction gas is the same as NH ₃ , the Ge (Ⅱ) source represented by the formula (18) can be used to form a phase change material film at a temperature lower than 300 ° C., ie, 280 ° C., 240 ° C., Can be formed. However, when using a Ge (Ⅵ) source that is not sterically opened, a phase change material film was not formed at a temperature lower than 300 캜. In the case of using the Ge (II) source represented by Chemical Formula 19, as in the case of using the Ge (II) source represented by Chemical Formula 18, a phase change material film is formed at a temperature lower than 300 ° C., ie, 280 ° C. and 240 ° C. Could. From these results, it can be seen that the deposition temperature of the phase change material layer can be reduced to less than 300 ° C. and further reduced to 200 ° C. when Ge (Ⅱ) source is used as compared with the case where the Ge (Ⅵ) .

On the other hand, when the reaction gas is H ₂ The phase change material layer can be formed at a temperature lower than 300 ° C, that is, at 280 ° C and 240 ° C, by using the Ge (Ⅱ) source represented by the formula (18). However, the phase change material film deposition rate at 280 ° C and 240 ° C was very small. The same result was obtained when the Ge (II) source represented by the above formula (19) was used. From these results, it can be seen that when the reaction gas is H ₂ It can be seen that the deposition rate of the phase change material layer using Ge (II) source can be improved even when the reaction gas is NH ₃ at a temperature lower than 300 ° C.

FIGS. 7A and 7B are photographs showing a phase change material film formed according to Experimental Example 2, FIGS. 8A and 8B are photographs showing a phase change material film formed according to Experimental Example 3, FIGS. 9A and 9B are photographs Are the photographs showing the phase change material film formed in accordance with the present invention.

7A, 7B, 8A, 8B, 9A and 9B, the reaction gas NH ₃ And the Ge (II) source represented by the formula (18), the phase change material film formed using the Ge (Ⅱ) source represented by the formula (18) is not only in the case where the deposition temperature is 280 ° C. (FIGS. 7A and 7B), 240 ° C. 9a and 9b), the side wall of the via hole can be cone-shaped without covering the upper portion of the via hole, and furthermore, the via hole can be filled without voids.

In conclusion, by reducing the deposition temperature of the phase change material film by using a Ge (II) source having improved reactivity, the grain size of the chalcogenide film can be reduced, and consequently, the chalcogenide film And furthermore, the contact holes can be filled without voids.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, This is possible.

Figure 1 is a graph illustrating a method for performing a set or reset programming for a phase change resistor.

2 is a flow chart showing a method of forming a Ge-containing phase change material film according to an embodiment of the present invention.

3 is a gas pulsing diagram for forming a Ge-Sb-Te film using a chemical vapor deposition method.

4 is a gas pulsing diagram for forming a Ge-Sb-Te film using atomic layer deposition.

5A and 5B are cross-sectional views illustrating a method of manufacturing a phase-change memory device according to an embodiment of the present invention.

6A, 6B, and 6C are cross-sectional views illustrating a method of manufacturing a phase-change memory device according to another embodiment of the present invention.

Figs. 7A and 7B are photographs showing a phase change material film formed according to Experimental Example 2. Fig.

8A and 8B are photographs showing a phase change material film formed according to Experimental Example 3.

FIGS. 9A and 9B are photographs showing a phase change material film formed according to Experimental Example 4. FIG.

Claims (25)

Supplying a reaction gas represented by the following formula (1) in a reaction chamber; Supplying a Ge (II) source as a first source into the reaction chamber; And And supplying a second source into the reaction chamber. &Lt; Formula 1 > NR ₁ R ₂ R ₃ Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , Si (CH ₃ ) ₃ , NH ₂ , NH CH ₃ ), N (CH ₃ ) ₂ , NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ . The method according to claim 1, Wherein the reactive gas is a reactive gas having an NH ₂ group. 3. The method of claim 2, Wherein the reactive gas is one selected from the group consisting of ammonia, primary amine, and hydrazine. The method according to claim 1, Wherein the Ge (II) source comprises an amide ligand, a phosphanido ligand, an alkoxide ligand, or a thiolate ligand. 5. The method of claim 4, Wherein the Ge (II) source is any one selected from the group consisting of the sources represented by the following Chemical Formulas 2 to 4: (2) R ₁ R ₂ X ₁ -Ge- X ₂ R ₃ R ₄ In Formula 2, X ₁ And X ₂ are each independently N or P, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen; A C ₁ to C ₁₀ alkyl group; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefinic groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylenic group of C ₂ to C ₁₃ ; Allenic group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); Amide ligand wherein each of NR ₅ R ₆ , R ₅ and R ₆ is independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group ); SiR ₇ R ₈ R _{9 wherein} R ₇ , R ₈ and R ₉ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or _two or more of R ₁ , R ₂ , R ₃ and R ₄ are chemically bonded to form a ring system. (3) R _{1 is} Y ₁ -Ge-Y ₂ R ₂ In Formula 3, Y ₁ And Y &lt; ₂ &gt; are each independently O or S, and R &lt; _{1 &} And R &lt; ₂ &gt; are each independently selected from the group consisting of hydrogen; Alkyl group of C ₁ ~ C _10; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefin groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylene group of C ₂ to C ₁₃ ; Allene group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); An amide ligand (NR ₃ R ₄ , R ₃ and R ₄ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allylene group); SiR ₅ R ₆ R _{7 wherein} R ₅ , R ₆ and R ₇ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or R ₁ and R ₂ are chemically bonded to form a ring system. &Lt; Formula 4 > R ₁ R ₂ X-Ge-YR ₃ In Formula 4, X is N or P, Y is O or S, R ₁ , R _2, and R ₃ are each independently hydrogen; Alkyl group of C ₁ ~ C _10; A C ₁ -C ₁₀ alkyl group in which CH ₃ is substituted by an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, N of the imine group, N of the amine group, O of the alkoxy group or O of the ketone group is a C ₁ -C ₁₀ alkyl group ; C ₂ to C ₁₂ olefin groups; A C ₃ to C ₁₂ olefin group in which CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group; CH ₃ is substituted with an imine group, an amine group, an alkoxy group or a ketone group, and N of the imine group, N of the amine group, O of the alkoxy group, or O of the ketone group is substituted with C ₃ -C ₁₂ olefin group; An acetylene group of C ₂ to C ₁₃ ; Allene group (CHCCH ₂ ); A cyano group (CN); NCX group (X is O, S, Se or Te); Azide ligand (N ₃ ); An amide ligand (NR ₄ R ₅ , R ₄ and R ₅ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group); SiR ₆ R ₇ R _{8 wherein} R ₆ , R ₇ and R ₈ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group) ; Or a combination thereof, or R ₁ , R ₂ And R &lt; ₃ &gt; are chemically bonded to form a ring system. delete delete delete The method according to claim 1, Wherein the second source is at least one source selected from the group consisting of Te source, Sb source, Bi source, As source, Sn source, O source, Au source, Pd source, Se source, Ti source, &Lt; / RTI &gt; delete delete The method according to claim 1, And supplying the carrier gas and the reaction gas into the reaction chamber while supplying the first source and the second source. delete Supplying a Ge (II) source as a first source into the reaction chamber; And And supplying a second source into the reaction chamber, Wherein the Ge (II) source is any one of the following Chemical Formulas 5 to 17: &Lt; Formula 5 >

In Formula 5, X ₁ and X ₂ are each independently N or P, of R _1, R _2, R ₃ and R ₄ is hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ of each independently An olefin group, an acetylene group or an allene group of C ₂ to C ₁₃ . (6)

In Formula 6, X ₁ and X ₂ are each independently N or P, and, R ₁ and R ₂ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ of An acetylene group or an allylene group of C &lt; ₁₃ &gt; &Lt; Formula 7 >

In Formula _{7, X 1, X 2,} X 3 and X ₄ are each independently N or _{P, R 1, R 2,} R 3, R 4, R 5 and R ₆ are independently hydrogen, C ₁ each An alkyl group having ₁ to ₁₀ carbon atoms, an olefin group having ₂ to ₁₂ carbon atoms, an acetylene group or an allene group having ₂ to ₁₃ carbon atoms. (8)

In Formula 8, X ₁ and X ₂ are each independently N or P, and, Y ₁ and Y ₂ are each independently O or _{S, R 1, R 2,} R 3, R 4, R 5, R 6 , R ₇ and R ₈ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group or an allene group. &Lt; Formula 9 >

Wherein X ₁ , X ₂ , X ₃ and X ₄ are each independently N or P and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allene group. &Lt; Formula 10 >

In Formula _{10, X 1, X 2,} X 3 and X ₄ are each independently N or _{P, R 1, R 2,} R 3, R 4, R 5 and R ₆ are independently hydrogen, C ₁ each An alkyl group having ₁ to ₁₀ carbon atoms, an olefin group having ₂ to ₁₂ carbon atoms, an acetylene group or an allene group having ₂ to ₁₃ carbon atoms. &Lt; Formula 11 >

In Formula 11, X ₁ and X ₂ are each independently N or P, Y ₁ and Y ₂ are each independently O or S, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, A C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allylene group. &Lt; Formula 12 >

In Formula 12, Y ₁ and Y ₂ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ of An acetylene group or an allylene group of C &lt; ₁₃ &gt; &Lt; Formula 13 >

In Formula 13, Y ₁ and Y ₂ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₂ olefin group, C ₂ ~ of An acetylene group or an allylene group of C &lt; ₁₃ &gt; &Lt; Formula 14 >

In Formula _{14, Y 1, Y 2,} Y 3 and Y ₄ are each independently O or _{S, R 1, R 2,} R 3, R 4, R 5 and R ₆ is hydrogen, C ₁ are each independently An alkyl group having ₁ to ₁₀ carbon atoms, an olefin group having ₂ to ₁₂ carbon atoms, an acetylene group or an allene group having ₂ to ₁₃ carbon atoms. &Lt; Formula 15 >

In Formula 15, X ₁ and X ₂ are each independently N or P, Y ₁ and Y ₂ are each independently O or S, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen, A C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, a C ₂ to C ₁₃ acetylene group, or an allylene group. &Lt; Formula 16 >

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently O or S, R ₁ and R ₂ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ An olefin group, an acetylene group or an allene group of C ₂ to C ₁₃ . &Lt; Formula 17 >

Wherein X is N or P, Y is O or S, R ₁ , R ₂ and R ₃ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₂ olefin group, An acetylene group or an allylene group of C ₂ to C ₁₃ . delete delete delete delete Loading a substrate on which a lower electrode is formed in a reaction chamber; Forming a Ge-containing phase change material film on the lower electrode by supplying a reactive gas represented by the following Formula 1, a first source Ge (II) source, and a second source into the reaction chamber loaded with the substrate; And And forming an upper electrode on the phase change material layer. &Lt; Formula 1 > NR ₁ R ₂ R ₃ Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , Si (CH ₃ ) ₃ , NH ₂ , NH CH ₃ ), N (CH ₃ ) ₂ , NH (C ₂ H ₅ ) or N (C ₂ H ₅ ) ₂ . delete delete delete delete delete delete

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